Molybdenum-containing lubricant additive compositions, and processes for making and using same

ABSTRACT

The invention relates to an improved process for producing organomolybdenum compositions with high molybdenum content that are highly useful as lubricant additives, in which the process involves reacting a fatty oil with a diamine, followed by reaction with a molybdenum source. The process of the present invention does not require a volatile organic solvent to promote molybdenum incorporation and produces an organomolybdenum composition having a high molybdenum content. In addition, the process can be conducted in the absence of sulfur and phosphorus-containing reactants.

TECHNICAL FIELD

[0001] The present invention relates to organomolybdenum compositionshaving high molybdenum content, which are useful as lubricant additives.The organomolybdenum compositions of the present invention are thereaction products of a fatty oil reacted with a diamine, followed byfurther reaction of the resulting intermediate with a molybdenum sourceto form the organomolybdenum product compositions, in which the processdoes not require a volatile organic solvent to promote and achieve highmolybdenum incorporation in the additive product, nor does it requiresulfur-containing or phosphorus-containing reactants nor post-reactionfiltration removal for unreacted molybdenum source reactant.

BACKGROUND OF THE INVENTION

[0002] Lubricating oils used in the internal combustion engines ofautomobiles or trucks are subjected to a demanding environment duringuse. Among other adverse effects, this environment can lead to oxidativedegradation of the oil. This oxidation of the oil is catalyzed by thepresence of certain impurities in the oil, such as iron compounds. Thisoxidation also is promoted by the elevated temperatures to which the oilis subjected during use. The oxidation of lubrication oils during use isusually controlled in part by the use of antioxidant additives, whichmay extend the useful life of the oil, particularly by reducing orinhibiting unacceptable increases in the viscosity of the oil.

[0003] Various molybdenum compounds have been used and proposed asperformance-enhancing additives for lubricant compositions. Forinstance, there are numerous examples in the patent literature whichdescribe the use of molybdenum additives variously as antioxidants,deposit control additives, anti-wear additives and friction modifiers,in lubricant compositions. A partial list of such patent referencesincludes, for example, U.S. Pat. Nos. 4,164,473, 5,840,672, 6,103,674,6,174,842, and U.S. Reissued Pat. No. RE37,363 E, among others.

[0004] The preparation of organomolybdenum additives generally requirescomplicated reaction steps that add considerable cost to themanufacturing of these additives. Examples of some costly processingsteps in this respect are as follows:

[0005] 1. The use of volatile organic compound (“VOC”) solvents, such astoluene, xylenes, 2-propanol, and dimethylformamide add considerablecost to the production of organomolybdenum compounds.

[0006] 2. Low levels of molybdenum incorporation into the lubricantadditive itself are achieved, which increases cost because higherconcentrations of the resulting organomolybdenum product/additive mustbe used in the oil to deliver the required level of molybdenum to thecrankcase package or finished oil. Ideally, it would be desirable toproduce these organomolybdenum products/additives having molybdenumcontents above 8 percent by weight, and preferably above 10 percent byweight.

[0007] 3. Filtration is generally required to remove unreacted inorganicmolybdenum. Unreacted molybdenum adds considerable cost to theproduction of organomolybdenum compounds because inorganic molybdenum isan expensive raw material.

[0008] 4. Other costly processing steps associated with prior schemesfor producing organomolybdenum components or lubricant additives includethe need for acid or base neutralizations, the use of expensivecatalysts or promoters, and water washes.

[0009] Examples of such prior processes for making organomolybdenumcomponents or lubricant additives are reported, for example, in thepatent literature as follows:

[0010] EP 1 136 496 discloses a product derived frommethylaminopropylamine (R contains 1 carbon), which shows limitedsolubility in oil, while products containing 6 or more carbons in the Rgroup have low molybdenum content (less than or equal to 8% undiluted).

[0011] EP 1 136 497 discloses molybdenum compounds derived fromcarboxylic acids and glycerides, which are relatively expensive.

[0012] U.S. Pat. No. 4,889,647 discloses molybdenum products that haverelatively low molybdenum contents, for example 6 percent by weight, orlower.

[0013] U.S. Pat. No. 6,103,674 discloses molybdenum products that havelow molybdenum contents, for example, 8 percent by weight or lower, andwhich contain sulfur.

[0014] Sulfur can be an undesirable component in engine oils. At hightemperatures and under severe conditions, even the less aggressive formsof sulfur can cause corrosion, and in some cases elastomeric sealincompatibility (e.g., rubber hardening). Ideally, therefore, molybdenumcompounds intended for use in lubricant engine oils should have minimalsulfur content.

[0015] U.S. Pat. No. 4,692,256 discloses a process for making anorganomolybdenum compound that requires neutralization steps and waterseparations in order to isolate the organomolybdenum compound. Whenwater is used as a promoter, as in U.S. Pat. No. 4,692,256, a filtrationis required to remove unreacted molybdenum. U.S. Pat. No. 5,137,647discloses a sulfur and phosphorous-free organomolybdenum complex oforganic amide, such as molybdenum containing compounds prepared from thereaction of fatty derivatives of 2-(2-aminoethyl) aminoethanol with amolybdenum source, in which the reaction temperature can be as high as160° C. The sole example provided therein has a reaction temperatureranging from 130° C. to 140° C., and a filtration is carried out. Also,the reaction product is filtered, which adds an additional processingstep.

[0016] U.S. Pat. No. 4,765,918 discloses molybdenum-containingcompositions derived from fatty oils, amines, and a sulfur source.

[0017] U.S. Pat. No. 5,412,130 discloses molybdenum products derivedfrom specially pre-treated fatty oils, e.g., treated by epoxidationfollowed by alkylation, that are reacted with molybdenum using a veryspecific fatty oil-derived catalyst. This special pre-treatment of thefatty oil adds considerable cost to the resulting product, making itimpractical for use in lubricants.

[0018] The above problems suggest a previously unfulfilled need in thelubricant additive and composition industry and related technologies foroil soluble, sulfur-free molybdenum additives having high molybdenumcontent and low tendency to discolor finished oils without the need touse volatile solvents and without the need to remove non-reactedmolybdenum. It has unexpectedly been found that the molybdenum additivesof the present invention provide the above benefits to lubricatingcompositions without the attendant problems.

SUMMARY OF THE INVENTION

[0019] The present invention is directed to unique organomolybdenumcompositions, which are especially useful as lubricant additives. Toform the organomolybdenum compositions of this invention, a fatty oil, adiamine and a molybdenum source are combined in the absence of avolatile organic solvent yet effective to form a high organo molybdenumcontent reaction product. This reaction product obtained also does nothave to be filtered to remove unreacted molybdenum source material.

[0020] In a more particular aspect, the present invention is directed toan organomolybdenum composition comprising the reaction product of afatty oil reacted with an aliphatic diamine, followed by furtherreaction of the resulting intermediate reaction product with amolybdenum source in the absence of volatile organic solvent and withoutneed for post-reaction filtering. In one preferred aspect, the firstprocess step is performed neat, while in the second process step a smallamount of water, but no volatile organic solvent is introduced orpresent during the molybdenum incorporation reaction, sufficient for themolybdenum source ingredient to go into solution such that reactionstill proceeds well.

[0021] In one further aspect, the diamine reactant used is amonsubstituted amine having high hydrocarbon character, such asrepresented by the following general structure:

[0022] where x is 1 or 2, and R is a hydrocarbon-containing groupcontaining at least about 6 carbon atoms. In one preferred aspect, the Rgroup also contains oxygen, such as where R represents analkyloxyalkylene group.

[0023] In another aspect, this invention provides a low cost process forproducing sulfur- and phosphorus-free organomolybdenum compositions withhigh molybdenum content. In one aspect, the high molybdenum content ofthe reaction products of the process of the invention comprises fromabout 8 wt % to about 15 wt % molybdenum content (Mo). In addition, theprocess improvements achieved do not require the use and presence of avolatile organic solvent to achieve highly effective incorporation ofmolybdenum in the reaction product, and the resulting reaction productalso does not require filtration to remove unreacted molybdenum sourcematerial such as molybdenum trioxide. The molybdenum-containinglubricant additives of the present invention are also very effective asantioxidants and deposit control additives in crankcase oils. Also, ithas unexpectedly been found that preparation of the organomolybdenumcompositions at reduced reaction temperatures according to anotheraspect of the present invention results in an improvement in the depositcontrol performance of the reaction product when used as an additive inengine oils. The molybdenum-containing lubricant additives of thepresent invention also are light colored complexes that are not prone todiscoloration even when used at high concentrations in crankcase oils.

DETAILED DESCRIPTION OF THE INVENTION

[0024] In an embodiment of the present invention, the reaction schemeused to prepare the molybdenum additives includes a two step process.The first included step involves preparing an organic ligand comprisedof an aminoamide/glycerol carboxylate mixture. This mixture is preparedby combining, mixing, contacting, or reacting (a) a fatty oil, vegetableoil, triglyceride or other glycerol ester of a higher fatty acid with(b) a mono-substituted alkylene diamine at an elevated temperature withheating. The second step involves carrying out the molybdenumincorporation.

[0025] Fatty Oils

[0026] Examples of preferred fatty or vegetable oils that may be used inthe process of the present invention include groundnut oil, coconut oil,linseed oil, palm kernel oil, olive oil, cottonseed oil, grapeseed oil,corn oil, canola oil, palm oil, peanut oil, safflower seed oil, sesameseed oil, caster oil, rapeseed oil (low or high erucic acids), soyabeanoil, sunflower oil, herring oil, sardine oil, lard, menhaden oil, hazelnut oil, walnut oil, and tallow, and mixtures thereof. These fatty orvegetable oils can include those compounds generally known astriglycerides, which have the general structure as shown below:

[0027] where R, R′ and R″ independently represent saturated orunsaturated aliphatic hydrocarbon groups having from about 8 to about 22carbon atoms, and preferably are hydrocarbon chains having about 12 toabout 22 carbon atoms. Mono- and diglycerides, either separately or inmixtures with one or more triglycerides, are also useful as fatty orvegetable oils in the present invention, in which the R, R′, or R″groups present have the same above meaning.

[0028] The Diamine

[0029] In order to improve solubility of the organomolybdenum product inbase oils and finished oils, it is important for the mono-substituteddiamine to have a high hydrocarbon character. For example, the diaminecan be represented by the following general structure:

[0030] where x is 1 or 2, and R is a hydrocarbon-containing groupcontaining a minimum of about 6 carbon atoms. R can be aliphatic oraromatic. R, in addition to the minimum of about 6 carbon atoms, mayalso contain oxygen, but preferably R does not include sulfur oradditional nitrogen. It is preferred that R contains a minimum of 10carbon atoms in order to further improve the organomolybdenum productsolubility in base oil. The most preferred R contains an oxygen inaddition to the carbons, such as where R is an alkyloxyalkylene group.Where R represents an alkyloxyalkylene group, R can be represented bythe structure —X₁—O—X₂, where X₁ is an alkylene of 2, 3 or 4 carbons andpreferably is propylene or ethylene, and X₂ is an alkyl moiety having 3to 30 carbon atoms, more preferably an alkyl moiety having 7 to 20carbon atoms, and where X₂ can be a straight or branched, saturated orpartially unsaturated hydrocarbon chain. In diamines in which R isrepresented by such an alkyloxyalkylene group, both high incorporationof molybdenum, e.g., greater that 8.0 wt. % molybdenum incorporation, into complexed product, as well as adequate oil-solubility are wellimparted to the reaction product. The use of a diamine including an Rgroup represented by —X₁—O—X₂ as defined herein in the reaction processmakes it possible to maximize the level of molybdenum incorporationlevels in the oil soluble reaction product while performing the processwithout the use of volatile organic processing solvents.

[0031] Examples of some mono-substituted diamines that may be usedinclude phenylaminopropylamine, hexylaminopropylamine,benzylaminopropylamine, octylaminopropylamine, octylaminoethylamine,dodecylaminopropylamine, dodecylaminoethylamine,hexadecylaminopropylamine, hexadecylaminoethylamine,octadecylaminopropylamine, octadecylaminoethylamine,isopropyloxypropyl-1,3-diaminopropane,octyloxypropyl-1,3-diaminopropane, decyloxypropyl-1,3-diaminopropane,isodecyloxypropyl-1,3-diaminopropane,dodecyloxypropyl-1,3-diaminopropane,tetradecyloxypropyl-1,3-diaminopropane,isodecyloxypropyl-1,3-diaminopropane,isododecyloxypropyl-1,3-diaminopropane,isotridecyloxypropyl-1,3-diaminopropane. Mono-substituted diaminesderived from fatty acids may also be used. Examples include N-cocoalkyl-1,3-propanediamine (Duomeen C), N-tallow alkyl-1,3-propanediamine(Duomeen T), and N-oleyl-1,3-propanediamine (Duomeen O), all obtainedfrom Akzo Nobel.

[0032] In order to produce an additive reaction product with a highmolybdenum content, it is preferred to use a molar ratio of diamine tofatty oil in the first process step varying from about 1.50:1 to 3:1. Amore preferred ratio is from about 1.75:1.0 to about 2.5:1.0.

[0033] The reaction between the fatty oil and mono-substituted diamineis carried out according to one embodiment at a temperature betweenabout 100 and about 150° C. by combining the two materials and heatingwith mixing and under a nitrogen atmosphere. The preferred reactiontemperature is between 110 and 130° C. Reaction times may vary from 1hour to 6 hours. A reaction solvent, such as an organic reactionsolvent, is not required.

[0034] As mentioned supra, the second included step of the process ofthe present invention involves carrying out the molybdenumincorporation, which is described in more detail below.

[0035] Molybdenum Source

[0036] A preferred molybdenum source is molybdenum trioxide. The use ofmolybdenum trioxide results in effective molybdenum incorporation intothe organic ligand made by the aforementioned first process step, and itproduces a reaction mass by the completion of the second step that doesnot require filtration if the reaction is performed properly accordingto guidance provided herein. Any purity grade of molybdenum trioxide maybe used but high purity molybdenum trioxide is thought more likely toproduce a product that does not require filtration.

[0037] Molybdenum Incorporation

[0038] A molybdenum source, such as molybdenum trioxide, and water areadded to an aminoamide/glycerol carboxylate reaction mass obtained fromthe first process step and maintained at approximately 80° C. The molarratio of molybdenum trioxide to diamine can vary from about 1:1.25 toabout 1.25:1, and is preferably between 1:1.25 and 1:1 in order tomaximize molybdenum content and at the same time reduce or eliminate thepresence of unreacted molybdenum trioxide, which thus reduces oreliminates the need for filtration. The amount of water used in thissecond step should be an amount sufficient to incorporate all themolybdenum trioxide into the aminoamide intermediate and is generallyequivalent to the amount of molybdenum trioxide used, but lower andhigher levels of water may be used. After addition of the molybdenumtrioxide and water the reaction components are slowly heated to refluxtemperature with gradual removal of water. Water may be removed byvacuum distillation. The reaction may be carried out at temperaturesranging from 100° C. to 150° C., however, it has been found thattemperatures below 140° C. are preferred for producing a molybdenumcompound that is highly effective as a deposit control additive. Themost preferred reaction temperature is below 130° C. The reactiongenerally requires 1 to 10 hours to remove all the water and this timewill vary depending on the reaction temperature selected and the levelof vacuum applied. During the water removal a diluent may be added toreduce the viscosity of the final product. However, a diluent is notrequired for the molybdenum incorporation. Preferred diluents includenon-volatile diluents such as aromatic, paraffinic, and naphthenicprocess oils and base oils as well as synthetic oils andpolyalphaolefins. A main advantage of this process is that a volatileorganic solvent, such as toluene or xylenes, is not required in thesecond step for the water removal procedure or otherwise, nor are suchorganic solvents even used in the preferred embodiment.

[0039] At the end of the reaction period, the mixture is cooled and maybe filtered to remove any unreacted molybdenum trioxide. Moreover, ifthe reaction is run optimally, filtration is not required, as tangibleamounts of unreacted molybdenum trioxide will not be present. That is,the reaction step of molybdenum incorporation goes essentially to 100%completion. It is preferred to produce a reaction mass with completemolybdenum incorporation so that no post-reaction filtration is requiredto remove any unreacted molybdenum source material such as molybdenumtrioxide. The product prepared by this process is a dark, amber wax orviscous liquid.

[0040] Further, when the molybdenum incorporation is performed at orbelow 130° C., improved deposit control in engine oils is achieved usingthe resulting additive product of the process of the invention.

[0041] The preferred combination of mono-substituted diamine,triglyceride, fatty oil or vegetable oil, and molybdenum trioxide, isthat which produces a molybdenum content, undiluted with oil, greaterthan 8 wt. %, and preferably between 10 wt. % and 15 wt. %.

[0042] It is also an unexpected discovery that carrying out themolybdenum incorporation reactions at reduced temperatures improves thedeposit control properties of the molybdenum product produced. This isdemonstrated in the examples provided herein. It is therefore preferredto carry out the molybdenum incorporation reactions between 80 and 140°C., more preferably between 100 and 125° C.

[0043] The high molybdenum content organomolybdenum compositions of thepresent invention are useful to improve deposit control, antioxidant,antiwear, and/or friction modifiying properties of lubricant oils, andlike materials. The inclusion of the present molybdenum compoundsgenerally removes the need for supplementary deposit control orantioxidants, antiwear additives and the like. However, a supplementarydeposit control, antioxidant, and/or antiwear additive may be includedin the finished oils including the molybdenum additives of the presentinvention that are less oxidatively stable or in oils that are subjectedto unusually severe conditions. The treat rates of the molybdenumadditives depend upon the desired finished lubricant properties,however, typically the additives are present in an amount so as toprovide at least about 50, and preferably from about 50 to about 1000ppm, of molybdenum to the finished product. The concentration ofmolybdenum in the lubricants according to the invention has noparticular upper limit, however, for economic reasons a maximum level ofabout 1000 ppm is generally preferred although not required.

[0044] As an important aspect of the present invention, a process formaking an organomolybdenum additive has been discovered which can beperformed in the absence of volatile organic solvent without sacrificingthe level of molybdenum incorporation or oil solubility of the reactionproduct. This process thus avoids the production and handling costs thatotherwise would be associated with using such additional chemicals inperforming the process. The language “absence of volatile organicsolvent” means no volatile organic solvent is intentionally introducedor otherwise permitted to be present with the diamine, fatty oil andintermediate reaction product during the process of the presentinvention in amounts that might exceed trace amounts, that is, theamount of volatile organic solvent present, if any, during the processis less than 3.0 wt. % of the total reactor contents. From thisstandpoint, the process of the present invention consists essentially ofthe reaction product of fatty oil, diamine, and molybdenum source.

[0045] In addition, the organomolybdenum compositions of the presentinvention can be prepared without introducing sulfur or phosphorus. Theorganomolybdenum complex reaction products are substantially sulfur-freein the sense that the reaction itself introduces no sulfur into thereaction product, although some negligible trace levels of sulfur whichare not part of the molybdenum product itself might be present due toimpurities or catalysts left behind from the manufacturing process.Preferably, the amount of any sulfur in the organomolybdenum reactionproduct is less than 0.05 wt. %.

[0046] Sulfur can cause corrosion and elastomeric nitrile sealcompatibility-hardening problems, among other things, while phosphoruscan reduce automobile catalyst compatibility such as when used incrankcase oil formulations. The organomolybdenum compositions of thepresent invention can be formed free or at least substantially free ofsulfur and phosphorus because no reactants including such materials areneeded, nor used in the preferred embodiments.

[0047] When formulated into a lubricating oil, the organomolybdenumadditives of the present invention optionally can be used in combinationtherein with one or more other additives including those typically usedin lubrication oils. Typical additives used in lubrication oils, whichoptionally can be used in this respect, include detergents, corrosioninhibitors, rust inhibitors, additional antioxidants, dispersants, foaminhibitors, additional antiwear agents, additional friction modifiers,demulsifiers, VI improvers, pour point depressants, zincdialkyldithiophopshates (ZDDP), and so forth. Examples of such optionalsupplemental additives are described, for example, in U.S. Pat. No.5,840,672, which teachings are incorporated herein by reference.

[0048] The organomolybdenum compositions of the present invention are“oil soluble” in the sense that they are oil-soluble or capable of beingsolubilized under normal blending or use conditions into a lubricationoil or diluent for the concentrate.

[0049] The overall composition of a lubricating oil including theorganomolybdenum additive such as described herein can varysignificantly based on the customer and specific application. Theadditive of this invention can be employed in a variety of lubricatingoil base stocks, such as derived from natural lubricating oils,synthetic lubricating oils or mixtures thereof. These oils includetypical crankcase lubrication oils for spark-ignited andcompression-ignited internal combustion engines, for example natural gasengines, automobile and truck engines, marine, and railroad dieselengines.

[0050] These oil base stocks can include, for example, hydrocracked baseoils; mineral oils such as paraffinic, naphthenic or mixtures thereof;vegetable oils; petroleum oils, oils derived from coal shale;silicon-based oils; halosubstituted hydrocarbon oils; esters ofdicarboxylic acids with alcohols; wax isomerate oils; polyalphaolefins,and mixtures thereof. In one preferred non-limiting embodiment, the baseoils used in forming the lubricating compositions of the presentinvention are characterized by the presence of a high level of saturatesand a very low level of sulfur, and include base oils referred to in thepetroleum additive industry as Group II and Group III base oils. Furtherdetails on such base oils are described, for example, in U.S. Pat. No.5,840,672, which teachings are incorporated herein by reference. In onenon-limiting illustration, the base oils generally contain greater thanor equal to 90% saturates, less than or equal to 0.03 weight percentsulfur and have a viscosity index of greater than or equal to about 80.The base oil typically has a viscosity generally of about 2 to about 15cSt at 100° C.

[0051] In one non-limiting embodiment, the lubricant oil can be aformulated oil comprising between about 75 to about 95 weight percent(wt %) of a base oil of lubricating viscosity, between 0 and 30 wt % ofa polymeric viscosity index improver, between about 5 and 15 wt. % of anadditional additive package and typically a sufficient amount ofmolybdenum complex to provide at least about 50 ppm of molybdenum to thefinished lubricant. The optional supplemental additives, for example,could be a supplemental detergent/inhibitor additive package and/orviscosity index improver. The present invention also encompasses theimproved lubricating oil compositions, which contain theorganomolybdenum additives of the present invention.

[0052] The organomolybdenum additives of the present invention can beused in lubricating oils such as crankcase oils for internal combustionengines, as well as gear lubricants, hydraulic fluids, automatictransmission fluids, turbine lubricants, engine fuels, compressor oils,lubricating greases, and so forth. The lubricating oil compositions ofthis invention can be made by adding the molybdenum compositions, andany supplemental additives, to an oil of lubricating viscosity. Themethod or order of component addition is not critical. Alternatively,the molybdenum compositions, along with any additional additives, can beadded to the oil as a concentrate.

EXAMPLES

[0053] The following examples further illustrate aspects of the presentinvention but do not limit the present invention.

[0054] The attached examples demonstrate that organomolybdenum additiveswith undiluted molybdenum contents between 8.1 wt % and 11.4 wt % areeasily produced using this process and inexpensive triglycerides as thefatty or vegetable oil reactant and starting material. It is possibleusing this process, and the right combination of diamine and vegetableoil, for example, to produce organomolybdenum additives with undilutedmolybdenum contents as high as 15 wt %. The examples described hereinalso show that molybdenum incorporations performed at reducedtemperature produce molybdenum additives with improved deposit controlproperties.

[0055] It has also been found that most of the organomolybdenumcompounds produced in the examples described herein did not requirefiltration to remove unreacted molybdenum trioxide. Examination offilters after the filtration process showed no evidence of collectedunreacted molybdenum trioxide or insolubles of any type in anyappreciable quantities. Thus filtration is typically not required in thepractice of the additive making process of the present invention.

[0056] The oil-soluble molybdenum-containing additives of the presentinvention may be used as antioxidants, deposit control additives,anti-wear additives, and/or friction modifiers. The table belowsummarizes treat rates and additive combinations for the variousapplications: TABLE 1 Recommended Performance Boosting Application TreatRange Additives Oil Type Antioxidant 75-250 Diphenylamines Passenger ppmMo (0.05-1.0%) Car and Sulfur Containing Additives Medium (0.2-1.0%)Speed Diesel Sulfurized Phenate Oils Detergents (0.3-3.0%) ZDDP(0.5-1.2%) Anti-wear 50-100 ZDDP Passenger ppm Mo Sulfur ContainingAdditives Car and Heavy Duty Diesel Oils Deposit 75-250 DiphenylaminesHeavy Duty Control ppm Mo (0.05-1.0%) Diesel and Sulfurized PhenateNatural Gas Detergents (0.2-3.0%) Engine Oils Friction 250-1000Antioxidants (0.1-1.0%) Passenger Modifier ppm Mo Organic FrictionModifiers Car Oils (0.3-1.0%)

EXAMPLE 1 Preparation of Sulfur-Free Organomolybdenum Additive (SampleNo. 1)

[0057] A. Preparation of Amide Organic Ligand Intermediate ReactionProduct RBD Canola Oil (250.0 g, 0.277 mol) was added to a 500 μL resinkettle equipped with a reflux condenser, an addition funnel, athermometer, a mechanical stirrer, and a heating mantle. Dry nitrogenwas passed into the reactor through the addition funnel, and out of thereactor through the reflux condenser. The Canola Oil was heated to 80°C. and isodecyloxypropyl-1,3-diaminopropane (135.0 g, 0.458 mol) wasadded dropwise over 45 minutes. During the amine addition the reactiontemperature was held at 80° C. The reaction mixture was then heated to125° C. and held at that temperature, under nitrogen and with sufficientagitation, for 5½ hours. The reaction was cooled overnight.

[0058] B. Molybdenum Incdrporation—Preparation of OrganomolybdenumDerivative Complex Product

[0059] The amide mixture intermediate reaction product, prepared asdescribed above, was heated to 80° C. and the molybdenum trioxide (66.0g, 0.459 mol) and water (35.0 g, 1.94 mol) are added. The reactionmixture rapidly rose to 95° C. The reaction mixture was then heated toreflux temperature and held at 111° C. for 30 minutes. Water wascollected to a reaction temperature of 130° C. Shell E-C 100 N processoil (96.6 g) was then added. Vacuum was applied and the remaining waterwas removed at 130° C. over a 5 hour period. The resulting product wascooled to 100° C. and filtered using a pressure filtration apparatus.The product was isolated as an amber viscous oil. Weight of ProductCollected=520 g. The physical and chemical properties of theorganomolybdenum product are as follows: Viscosity@100° C.=71.93 cSt,Nitrogen Content=2.611 wt %, Molybdenum Content=8.298 wt %, CalculatedMolybdenum Undiluted=10.1 wt %, TBN (ASTM D 2896)=32.3 mg KOH/g, IRCarbonyl Stretches=1738 cm⁻¹, 1639 cm⁻¹.

[0060] Preparation of Organomolybdenum Additive Sample Nos. 2-9

[0061] Additional samples of sulfur- and phosphorus-freeorganomolybdenum additives were prepared in a manner analogous to thatdescribed above, with modifications, reagents, reaction conditions, andproperties as defined in the table below: TABLE 2 Additive Sample No. 23 4 5 6 7 8 9 Canola Oil (g) 225.0 270.0 225.0 225.0 300.0 250.0 — 337.5Coconut Oil (g) — — — — — — 190.0 — Diamine (g)¹ — — 135.0 135.0 123.3135.0 135.0 202.5 Diamine (g)² 115.0 114.0 — — — — — — MoO₃ (g) 50.049.2 51.0 65.0 59.3 71.5 66.0 98.0 Water (g) 25.0 25.0 25.0 35.0 30.035.0 35.0 52.5 Process Oil (g) 127.0 76.2 None 104.0 None 140.2 156.6175.0 Yield (g) 497 492 377 499 456 545 530 774 Mo Rx Temp. Range 80-12080-120 80-120 80-125 80-130 80-140 80-140 80-140 (° C.) Visc. @ 100° C.(cSt) 55.0 66.3 100.4 78.9 103.2 53.8 55.1 67.5 Molybdenum (wt %) 6.616.62 8.39 8.28 8.13 8.34 8.06 8.24 Calc Mo Undiluted 8.8 7.8 8.4 10.48.1 11.0 11.4 10.6 (wt %) Nitrogen (wt %) 2.40 2.44 3.40 2.66 2.65 2.382.64 — TBN (mg KOH/g) 43.1 39.9 47.4 39.6 36.0 28.3 30.8 34.2 IRcarbonyl (cm-1) 1739, 1739, 1738, 1739, 1739, 1739, 1738, 1738, 1639 1640  1639  1640 1639  1639  1638  1638 

[0062] As an additional additive sample which was prepared, sample no.10, 2-(2-aminoethylamino)ethanol was instead used as the diaminereactant. For this additional study, Step A, the preparation of theamide organic ligand was conducted in the same manner as described aboveexcept that 225.0 g (0.25 mol) of canola oil was used as the fatty oilreactant, and 47.7 g (0.458 mol) of 2-(2-aminoethylamino)ethanol wasused as the diamine reactant. In step B, the molybdenum incorporationstep, the amide mixture intermediate reaction product obtained from stepA was heated to 80° C. and the molybdenum trioxide (65.0 g, 0.45 mol)and water (35.0 g, 1.94 mol) are added. The reaction mixture rapidlyrose to 91° C. The reaction mixture was heated to reflux temperature toremove water. Excessive foaming was observed to occur at 102° C. Heatingwas continued and the foaming was observed to get considerably worse.Two drops of Dow Corning Fluid 20% was added to the reaction in anattempt to reduce the foaming. No reduction in foaming was observed. Atthis point the foaming was to the extent that the reaction mass startedto climb out of the reactor, at which point the heating procedure wasterminated. The heating mantle was removed while the reactiontemperature was still above 100° C. Considerable foam was observed inthe reaction product mass. Thus, the additive samples 1-9, which wereperformed without an organic reaction solvent and did not require anyextraneous antifoaming agents, are preferable over additive sample 10.

EXAMPLE 2

[0063] Evaluation of Organomolybdenum Additives in the CaterpillarMicro-Oxidation Test

[0064] Organomolybdenum complexed product samples 1-9, as prepared inExample 1, were evaluated as additives in a modified version of theCaterpillar Micro-Oxidation Test (CMOT). Each additive was added to aseparate amount of SAE grade 15W-40 fully formulated crankcase oilcontaining approximately 1000 ppm of phosphorus derived from ZDDP and0.5 weight % of an alkylated diphenylamine antioxidant. This providedtest Oils 1-9. A Comparison Oil was also tested in which the crankcaseoil contained no molybdenum additive. The particular organomolybdenumcomplexed product among samples 1-9 used in each sample of base oil isindicated in Table 3. The additive treat levels were such thatapproximately 160 to 170 ppm of molybdenum was delivered to therespective finished Oils 1-9. For additives in the 8% molybdenum contentrange, this corresponds to 0.20 wt % of additive added to thelubricating oil formulation. For additives in the 6.5% content range,this corresponds to 0.25 wt % of additive content in the lubricating oilformulation.

[0065] The Micro-Oxidation Test is a commonly used technique forevaluating the deposit forming tendencies of a wide variety of passengercar and diesel lubricants as well as mineral and synthetic basestocks.The test measures the oxidative stability and deposit forming tendenciesof lubricants under high temperature thin-film oxidation conditions. Theability to easily vary test conditions and the flexibility of presentingtest results makes it a valuable research tool for screening a widevariety of lubricant products. In this test, a thin-film of finished oilis accurately weighed onto an indented low carbon steel sample holdersitting in a glass impinger tube. The sample, coupon and impinger tubeassembly is then immersed in a high temperature bath. Dry air is passed,at a specific rate, through the impinger tube, over the oil sample, andout of the impinger tube to the atmosphere. At specific time intervalsthe carbon steel sample holders are removed from the high temperaturebath, rinsed with solvent to remove any remaining oil, and oven dried.The solvent washes are filtered to collect any deposits that dislodgefrom the carbon steel holders. The sample holders and collected depositsare weighed to determine the amount of deposit formed at the samplinginterval. Results are reported as the percent of oil sample formingdeposit at a specific time interval. The induction time to depositformation can also be determined by calculating the intercept betweenthe baseline formed where minimal deposits are seen, and the slopeformed where a rapid rise in deposit formation is seen. Longer inductiontimes correspond to improved deposit control. Another parameter of valuein this test is the Performance Index (PI). The Performance Indexrepresents the reduction in deposit formation of the additized finishedoil over the entire sampling range of testing versus the baselinefinished oil over the same sampling range. The formula for calculatingPI is as follows:

PI=[((area of baseline oil/area of additized oil)−1)×100].

[0066] A larger Performance Index (PI) corresponds to improved depositcontrol.

[0067] The test conditions used to evaluate the test oils 1-9 are asfollows: gas=dry air, flow=20 cc/minute, temperature=230° C., samplinginterval=50, 60, 70, 80, 90, 100, 110, 120 minutes, samplesize=approximately 20 microL accurately weighed.

[0068] The deposit control results, as reported in percent deposits (wt%), for the tested oils containing the respective organomolybdenumcompounds are shown in the table below: TABLE 3 Percent Deposits (wt. %dep's) as a Function of Time Test Oil Comp. Oil 1 Oil 1 Oil 2 Oil 3 Oil4 Oil 5 Oil 6 Oil 7 Oil 8 Oil 9 Additive Sample No. No Mo Additive 2 3 14 5 6 7 8 9 Time wt. % wt. % wt. % wt. % wt. % wt. % wt. % wt. % wt. %wt. % (min) dep's dep's dep's dep's dep's dep's dep's dep's dep's dep's 50 4.4 1.4 1.9 1.1 2.1 4.2 2.0 2.6 1.3 3.2, 3.1  60 5.4 2.2 2.0 4.6 4.24.2 2.1 3.5 1.4 3.4, 3.2  70 15.3 2.3 2.4 6.2 4.7 4.3 2.2 3.5 1.9 3.4,3.4  80 16.4 2.8 2.6 6.3 4.8 4.3 2.6 3.9 2.1 3.7, 4.1  90 19.9 2.9 3.96.6 4.8 7.8 6.1 4.4 6.4 8.9, 8.3 100 21.4 2.9 10.8 9.0 4.8 10.3 11.017.1 8.8 18.2, 19.5 110 30.5 6.6 11.2 14.2 4.8 8.8 19.9 15.7 12.7 21.6,16.1 120 28.8 6.2 11.0 20.0 14.7 8.8 19.1 15.7 20.5 22.5, 15.6 Onset toDeposit Formation Min 53 101 89 96 111 80 82 90 82 81, 80 PerformanceIndex (PI) = [((area No Mo/area plus Mo) − 1) × 100] PI 421 210 109 216170 119 114 158 67, 94

[0069] Thus, the molybdenum-containing compositions of the presentinvention demonstrate a clear trend toward improvement in depositcontrol in an engine. Also shown is a significant reduction in depositswhen the molybdenum additives are prepared at lower reactiontemperatures.

EXAMPLE 3

[0070] Evaluation of Organomolybdenum Additives for Oil Coloration

[0071] A color and visual solubility were determined for the molybdenumcomplexed compounds of sample nos. 1-8, as described in Example 1, usinga paraffinic process oil diluent (PO#5). The color method was ASTM D1500. Color results are reported to the nearest one-half unit match onthe D1500 color scale. The treat levels were 1 wt. % for each testedsample, in which the treat level is based upon the amount (weightpercent) of the molybdenum compound added to the process oil, not theamount of molybdenum delivered to the process oil. An additional sample,sample no. 11, was prepared and tested in a similar manner forsolubility and color in which the organomolybdenum complexed productused was prepared in the manner described for additive Sample M6 asdescribed in European published patent application EP 1 136 496 A1. TheM6 additive involves the reaction product of 2-(2-aminoethylamino)ethanol and canola oil in which an organic reaction solvent is usedduring molybdenum incorporation.

[0072] The color and oil solubility results observed for these tests aresummarized below in Table 4. The higher the D1500 color value reported,the greater the darkening of the process oil that has occurred onaccount of the addition of the organomolybdenum additive. TABLE 4Additive Sample No. 1 2 3 4 5 6 7 8 11 D1500 1.5 1.0 1.0 1.5 1.5 1.5 2.5N/A 3.5 Color in PO #5 Solubility in yes yes yes yes yes yes yes no yesPO #5

[0073] From an examination of the results in Table 4, it is apparentthat that the molybdenum compounds made with diamine reactant in whichthe R group substituent, with reference to the diamine chemicalstructure described above herein, was an alkyloxyalkylene group, such asin samples 1-7, had the optimal color properties. It also is apparentthat the molybdenum compounds made with canola oil reactant (i.e., inwhich the R, R′ and R″ hydrocarbon chains therein are in the range ofC₁₂ to C₂₂, with reference to the fatty oil chemical structure describedabove herein) had excellent oil solubility.

[0074] Other embodiments of the present invention will be apparent tothose skilled in the art from consideration of the specification andpractice of the invention disclosed herein. It is intended that thespecification and examples be considered as exemplary only, with a truescope and spirit of the invention being indicated by the followingclaims. It is to be understood that both the foregoing generaldescription and the following detailed description are exemplary andexplanatory only and are intended to provide further explanation of thepresent invention, as claimed This invention is susceptible toconsiderable variation in its practice. Accordingly, this invention isnot limited to the specific exemplifications set forth hereinabove.Rather, this invention is within the spirit and scope of the appendedclaims, including the equivalents thereof available as a matter of law.

[0075] The patentee does not intend to dedicate any disclosedembodiments to the public, and to the extent any disclosed modificationsor alterations may not literally fall within the scope of the claims,they are considered to be part of the invention under the doctrine ofequivalents.

What is claimed is:
 1. A composition comprising the reaction product ofa fatty oil, a diamine, and a molybdenum source in which the reactionproduct is formed in the absence of volatile organic solvent.
 2. Thecomposition according to claim 1, wherein molybdenum source is molybdeumtrioxide.
 3. The composition according to claim 1, wherein the fatty oilis selected from a vegetable oil and a triglyceride, or a mixturethereof.
 4. The composition according to claim 1, wherein the fatty oilis selected from groundnut oil, coconut oil, linseed oil, palm kerneloil, olive oil, cottonseed oil, grapeseed oil, corn oil, canola oil,palm oil, peanut oil, safflower seed oil, sesame seed oil, caster oil,rapeseed oil, soyabean oil, sunflower oil, herring oil, sardine oil,lard, menhaden oil, hazel nut oil, walnut oil, and tallow, and mixturesthereof.
 5. The composition according to claim 1, wherein the fatty oilis a triglyceride having the formula:

wherein R, R′, and R″ each independently represents a saturated orunsaturated hydrocarbon chain group having about 8 to about 22 carbonatoms.
 6. The composition according to claim 1, wherein the vegetableoil comprises canola oil.
 7. The composition according to claim 1,wherein the diamine is selected from phenylaminopropylamine,hexylaminopropylamine, benzylaminopropylamine, octylaminopropylamine,octylaminoethylamine, dodecylaminopropylamine, dodecylaminoethylamine,hexadecylaminopropylamine, hexadecylaminoethylamine,octadecylaminopropylamine, octadecylaminoethylamine,isopropyloxypropyl-1,3-diaminopropane,octyloxypropyl-1,3-diaminopropane, decyloxypropyl-1,3-diaminopropane,dodecyloxypropyl-1,3-diaminopropane,tetradecyloxypropyl-1,3-diaminopropane,isodecyloxypropyl-1,3-diaminopropane,isododecyloxypropyl-1,3-diaminopropane,isotridecyloxypropyl-1,3-diaminopropane, mono-substituted diaminesderived from fatty acids, N-coco alkyl-1,3-propanediamine, N-tallowalkyl-1,3-propanediamine, and N-oleyl-1,3-propanediamine, and mixturesthereof.
 8. The composition according to claim 1, wherein the diaminehas the chemical structure

wherein x is 1 or 2 and R is an alkyl or alkyloxyalkylene group.
 9. Thecomposition according to claim 8, wherein R has at least 10 carbonatoms.
 10. The composition according to claim 8, wherein R furthercontains oxygen and is devoid of sulfur and nitrogen.
 11. Thecomposition according to claim 8, wherein R represents analkyloxyalkylene group.
 12. The composition according to claim 8,wherein R is represented by the structure —X₁—O—X₂, wherein X₁ is analkylene of 2, 3 or 4 carbons, and X₂ is an alkyl moiety having 3 to 30carbon atoms, and where X₂ can be a straight or branched, saturated orpartially unsaturated hydrocarbon chain.
 13. The composition accordingto claim 1, wherein the molar ratio of diamine to fatty oil is fromabout 1.5:1 to about 3:1.
 14. The composition according to claim 1,wherein the molar ratio of molybdenum to diamine is from about 1:1.25 toabout 1.25:1.
 15. The composition according to claim 1 containing lessthan 0.05 weight percent sulfur.
 16. The composition according to claim1 having a molybdenum content of from about 8.1 wt % to about 15 wt %.17. The composition according to claim 1 having a molybdenum content offrom 10.0 wt % to 15.0 wt %.
 18. An oil soluble composition comprisingthe reaction product of a fatty oil, a diamine, and a molybdenum source,wherein the diamine has the chemical structure:

wherein x is 1 or 2, and R is an alkyloxyalkylene group represented by—X₁—O—X₂, wherein X₁ is an alkylene of 2, 3 or 4 carbons, and X₂ is analkyl moiety having 3 to 30 carbon atoms, and wherein the fatty oilcomprises a triglyceride having fatty acid moieties, and said fatty acidmoieties comprise C₁₂ to C₂₂ hydrocarbon chains.
 19. The oil solublecomposition according to claim 18, wherein the molybdenum sourcecomprises molybdenum trioxide.
 20. The oil soluble composition accordingto claim 18, wherein x is 2, X₁ is 2, 3 or 4, and X₂ is an alkyl grouphaving 3 to 20 carbon atoms.
 21. The oil soluble composition accordingto claim 18, wherein the molar ratio of diamine to fatty oil is fromabout 1.5:1 to about 3:1.
 22. A composition according to claim 1, saidcomposition diluted with a process, mineral or synthetic oil.
 23. Alubricating oil composition comprising a major amount of an oil oflubricating viscosity, and a minor amount of a composition according toclaim 1 present in an amount sufficient to provide at least 50 ppm ofmolybdenum in the lubricating oil composition.
 24. A compositionaccording to claim 18, said composition diluted with a process, mineralor synthetic oil.
 25. A process for preparing a molybdenum-containingcomposition, comprising reacting a fatty oil, a diamine, and amolybdenum source, in the absence of volatile organic solvent.
 26. Theprocess according to claim 25, which comprises: (a) reacting a fatty oilwith a diamine to form an intermediate reaction mixture, and (b) addinga molybdenum source to thus obtained intermediate reaction mixture,wherein (a) and (b) are performed without introducing volatile organicsolvent.
 27. The process according to claim 26, wherein the intermediatereaction mixture comprises an aminoamide/glycerol carboxylate mixtureprepared by combining a glycerol ester of a fatty acid selected from afatty oil, vegetable oil, triglyceride, or a mixture thereof, with amono-substituted alkylene diamine.
 28. The process according to claim27, further comprising incorporating molybdenum into the intermediatereaction mixture by combining a molybdenum source with theaminoamide/glycerol carboxylate mixture.
 29. The process according toclaim 27, further comprising combining and heating the glycerol ester ofa fatty acid and the mono-substituted alkylene diamine with mixing at atemperature between about 100 degrees Celsius and about 150 degreesCelsius.
 30. The process according to claim 27, wherein the molybdenumsource is molybdenum trioxide.
 31. The process according to claim 27,wherein the molybdenum source and water are combined with theaminoamide/glycerol carboxylate mixture for a time and at a temperaturesufficient to produce a molybdenum-containing reaction product.
 32. Theprocess according to claim 31, wherein the time is from 1 to about 10hours and the temperature is from about 100 degrees Celsius to about 150degrees Celsius.
 33. A composition produced by the process of claim 26.34. The composition of claim 33, wherein the composition contains lessthan 0.05 wt % sulfur.
 35. The composition of claim 33, wherein thecomposition comprises from 10.0 wt % to 15.0 wt % molybdenum.
 36. Thecomposition of claim 33, wherein the composition comprises between 8.1wt % and 11.4 wt % molybdenum.
 37. A process of lubricating a crankcasecomprising adding the composition of claim 1 to a crankcase.
 38. Acrankcase lubricated with a composition of claim 1.